EP1390438B1 - Gefrierschutzmittelkonzentrate enthaltend den farbstoff c.i. reactive violet 5 - Google Patents

Gefrierschutzmittelkonzentrate enthaltend den farbstoff c.i. reactive violet 5 Download PDF

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Publication number
EP1390438B1
EP1390438B1 EP02740549A EP02740549A EP1390438B1 EP 1390438 B1 EP1390438 B1 EP 1390438B1 EP 02740549 A EP02740549 A EP 02740549A EP 02740549 A EP02740549 A EP 02740549A EP 1390438 B1 EP1390438 B1 EP 1390438B1
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EP
European Patent Office
Prior art keywords
concentrate
weight
total amount
acid
alkali metal
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP02740549A
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German (de)
English (en)
French (fr)
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EP1390438A1 (de
Inventor
Bernd Wenderoth
Ladislaus Meszaros
Uwe Nitzschke
Stefan Dambach
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids

Definitions

  • the present invention relates to new antifreeze concentrates based on alkylene glycols or their derivatives or of glycerin, containing the dye Color Index ("C.I.") Reactive Violet 5 (Color Index No. 18097). Furthermore concerns ready-to-use aqueous coolant compositions, which the anti-freeze concentrates mentioned include. The invention also relates to the use of these Antifreeze concentrates for the production of aqueous coolant compositions for internal combustion engines.
  • C.I. Color Index
  • Reactive Violet 5 Color Index No. 18097
  • Antifreeze concentrates for the cooling circuits of internal combustion engines for example in automobiles, mostly contain Alkylene glycols, especially ethylene glycol or propylene glycol, as Main component. They are used in the cooling system Diluted water and should not only protect against frost but also for good Ensure heat dissipation.
  • Alkylene glycol / water mixtures are at operating temperatures of internal combustion engines very corrosive. That is why the different Metals such as steel, cast iron, copper, brass, Aluminum, magnesium and their alloys as well as solder metals such as for example, solder that can occur in the cooling system the use of corrosion inhibitors sufficiently before the most diverse Types of corrosion, e.g. B. pitting corrosion, crevice corrosion, Erosion or cavitation.
  • solder metals such as for example, solder that can occur in the cooling system the use of corrosion inhibitors sufficiently before the most diverse Types of corrosion, e.g. B. pitting corrosion, crevice corrosion, Erosion or cavitation.
  • Antifreeze concentrates and coolants are becoming Avoiding confusion with other supplies from Motor vehicles, such as windshield washer fluids or Brake fluids, almost always by adding a dye inked.
  • the coloring should also be during and after the Use in the cooling system to be recognizable.
  • C.I. Direct Blue 199 C.I. 74190
  • C.I. Direct Blue 86 C.I. 74180
  • C.I. Acid green 25 C.I. 61570
  • C.I. Acid Yellow 73 C.I. 45350
  • uranine Sodium fluorescein
  • C.I. Acid Green 25 is used in the Usually with C.I. Acid Yellow 73 or combined with uranine, which makes a fluorescent green color is obtained.
  • a yellow dye is often also C.I. Acid Yellow 221 and as a red dye C.I. Basic Violet 10 (C.I. 45170) used.
  • blue dyes are used a 1-amino-4-anilino-anthraquinone structure as a coloring agent described for coolant compositions.
  • US-A 5 725 794 (2) recommends coolant compositions which polyoxyalkylene-substituted reactive dyes contain, which is improved by the polymer substituent should have thermal stability; for example Reactive dyes such as C.I. Basic Violet 3 or C.I. Reactive Violet 5 targeted in a chemical reaction with polyoxyalkylene amines or reacted with polyoxyethylene-dimethylsiloxane copolymers.
  • Reactive dyes such as C.I. Basic Violet 3 or C.I. Reactive Violet 5 targeted in a chemical reaction with polyoxyalkylene amines or reacted with polyoxyethylene-dimethylsiloxane copolymers.
  • EP-B 864 616 (3) there is also an implementation such reactive dyes with polyoxyethylene-dimethylsiloxane copolymers and their use in coolant compositions taught.
  • the teachings of (2) and (3) are particularly disadvantageous compared to the unsubstituted reactive dyes the additional synthesis step and the non-commercial availability such dyes
  • thermostable dyes that leaks in the cooling system after drying, no colored ones but at most colorless residues on metal surfaces form.
  • the present invention thus relates to antifreeze concentrates based on alkylene glycols or their derivatives or of glycerol containing 0.0005 to 0.1% by weight, preferably 0.001 to 0.05% by weight, in particular 0.002 to 0.02 % By weight of the dye C.I. Reactive Violet 5 (Color Index No. 18097), based on the total amount of the concentrate.
  • C.I. Reactive Violet 5 (Color Index No. 18097) is the copper complex of 5- (acetylamino -) - 4-hydroxy-3 - [[2-hydroxy-4 - [[2- (sulfooxy) ethyl] sulfonyl] phenyl] azo] -2,7-naphthalenedisulfonic acid. Its CAS Registry Number is 12226-38-9.
  • C.I. Reactive Violet 5 is in the antifreeze concentrate in non-derivatized form, i.e. such as it is commercially available.
  • the familiarization happens such that chemical reactions with components of the Antifreeze concentrate - at least before filling into the cooling system - must be excluded.
  • the present invention therefore also relates to a method for the production of antifreeze concentrates, which is characterized in that the dye C.I. Reactive Violet 5 (Color Index No. 18097) in an amount of 0.0005 to 0.1% by weight, preferably 0.001 to 0.05% by weight, in particular 0.002 to 0.02% by weight, based on the total amount of the concentrate, in antifreeze concentrates based on alkylene glycols or their derivatives or of glycerin.
  • the Familiarization usually takes place before the ready-to-use is generated aqueous coolant compositions from the concentrates or before filling the ready-to-use aqueous solution Coolant compositions in the cooling system.
  • the compounds of groups a) to g) are in the Rule around corrosion inhibitors.
  • Suitable linear or branched chain aliphatic or cycloaliphatic monocarboxylic acids a) are, for example, propionic acid, pentanoic acid, hexanoic acid, cyclohexylacetic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, decanoic acid, undecanoic acid or dodecanoic acid.
  • Aromatic monocarboxylic acid a) is particularly suitable benzoic acid, in addition there are, for example, C 1 -C 8 -alkylbenzoic acids such as o-, m-, p-methylbenzoic acid or p-tert-butylbenzoic acid and hydroxyl-containing aromatic monocarboxylic acids such as o-, m- or p-Hydroxybenzoic acid, o-, m- or p- (hydroxymethyl) benzoic acid or halobenzoic acids such as o-, m- or p-fluorobenzoic acid into consideration.
  • C 1 -C 8 -alkylbenzoic acids such as o-, m-, p-methylbenzoic acid or p-tert-butylbenzoic acid
  • hydroxyl-containing aromatic monocarboxylic acids such as o-, m- or p-Hydroxybenzoic acid, o-, m- or
  • di- or tricarboxylic acids b) are malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, Dicyclopentadienedicarboxylic acid, phthalic acid, terephthalic acid and triazine-triiminocarboxylic acids such as 6,6 ', 6' '- (1,3,5-triazine-2,4,6-triyltriimino) trihexanoic acid.
  • All of the carboxylic acids of groups a) and b) mentioned are as Alkali metal salts, especially as sodium or potassium salts, or as ammonium salts or substituted ammonium salts (amine salts) before, e.g. B. with ammonia, trialkylamines or trialkanolamines.
  • Typical examples of corrosion inhibitors mentioned under c) are sodium tetraborate (borax), disodium hydrogen phosphate, trisodium phosphate, Sodium metasilicate, sodium nitrite, sodium nitrate, Magnesium nitrate, sodium fluoride, potassium fluoride, magnesium fluoride and sodium molybdate.
  • alkali metal silicates are also used, they are expedient by conventional organosilicophosphonates or organosilicosulfonates stabilized in usual amounts.
  • aliphatic, cycloaliphatic or aromatic amines d) with 2 to 15, preferably 4 to 8 carbon atoms, which additionally contain ether oxygen atoms, in particular 1 to 3 ether oxygen atoms, or Hydroxyl groups, in particular 1 to 3 hydroxyl groups, contain can come, for example, ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, sec.-butylamine, tert.-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, isononylamine, Di-n-propylamine, diisopropylamine, di-n-butylamine, mono-, Di- and triethanolamine, piperidine, morpholine, aniline or benzylamine in question. Aliphatic and cycloaliphatic amines d) are usually saturated.
  • the heterocycles e) are, for example, mononuclear five- or six-membered systems with 1, 2 or 3 nitrogen atoms or with a nitrogen atom and a sulfur atom, which can be benzanellated. Two-core systems consisting of five- and / or six-membered partial rings with typically 2, 3 or 4 nitrogen atoms can also be used.
  • the heterocycles e) can additionally carry functional groups, preferably C 1 -C 4 alkoxy, amino and / or mercapto.
  • the heterocyclic backbone can of course also carry alkyl groups, especially C 1 -C 4 alkyl groups.
  • heterocycles e) are benzotriazole and tolutriazole (Tolyltriazole), hydrogenated tolutriazole, 1H-1,2,4-triazole, Benzimidazole, benzthiazole, adenine, purine, 6-methoxypurine, indole, Isoindole, isoindoline, pyridine, pyrimidine, 3,4-diaminopyridine, 2-aminopyrimidine and 2-mercaptopyrimidine.
  • tetra- (C 1 -C 8 -alkoxy) silanes f) are tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane or tetra-n-butoxysilane.
  • the amides g) can optionally be alkyl-substituted on the nitrogen atom of the amide group, for example by a C 1 -C 4 -alkyl group.
  • Aromatic or heteroaromatic backbones of the molecule can of course also carry such alkyl groups.
  • One or more, preferably one or two, amide groups can be present in the molecule.
  • the amides can carry additional functional groups, preferably C 1 -C 4 alkoxy, amino, chlorine, fluorine, hydroxy and / or acetyl, in particular such functional groups are found as substituents on aromatic or heteroaromatic rings present.
  • inhibitor components mentioned to g) can, for example, also soluble salts of magnesium of organic acids, e.g. B. magnesium benzene sulfonate, Magnesium methanesulfonate, magnesium acetate or magnesium propionate, Hydrocarbazoles or quaternized imidazoles, such as those in the DE-A 196 05 509 are described, in usual amounts as others Inhibitors are used.
  • Antifreeze concentrates according to the invention are preferred Carboxylic acids of groups a) and / or b) and / or heterocycles of group e) also used.
  • Embodiment contain the antifreeze concentrates according to the invention in addition to the dye 0.05 to 5% by weight, in particular 0.5 to 3% by weight, of two different ones Carboxylic acids from groups a) and / or b) and 0.05 up to 5% by weight, in particular 0.1 to 0.5% by weight, of one or more Heterocycles from group e).
  • carboxylic acids can be used for example mixtures of an aliphatic monocarboxylic acid and an aliphatic dicarboxylic acid, from an aromatic Monocarboxylic acid and an aliphatic dicarboxylic acid, from one aliphatic monocarboxylic acid and an aromatic monocarboxylic acid, from two aliphatic monocarboxylic acids or from two aliphatic Dicarboxylic acids are used.
  • Heterocycles are particularly suitable for benzotriazole and tolutriazole.
  • the pH of the antifreeze concentrates according to the invention is usually in the range from 4 to 11, preferably 4 to 10, in particular 4.5 to 8.5.
  • the desired pH can be adjusted optionally also by adding alkali metal hydroxide, Ammonia or amines set for formulation, solid Sodium or potassium hydroxide and aqueous sodium or potassium hydroxide solution are particularly suitable for this.
  • Carboxylic acids to be used are expediently the same as corresponding alkali metal salts added to automatically lie in the desired pH range. However, the carboxylic acids can also be added as free acids and then neutralize with alkali metal hydroxide, ammonia or amines and set the desired pH range.
  • Antifreeze concentrates are suitable Alkylene glycols and their derivatives as well as glycerin, in particular Propylene glycol and especially ethylene glycol.
  • glycerin in particular Propylene glycol and especially ethylene glycol.
  • glycols and glycol ethers into consideration, e.g. B. Diethylene glycol, dipropylene glycol and monoethers of glycols such as the methyl, ethyl, propyl and butyl ether of ethylene glycol, Propylene glycol, diethylene glycol and dipropylene glycol. It can also mixtures of the glycols and glycol ethers mentioned Mixtures of these glycols with glycerin and optionally these glycol ethers can be used.
  • the invention is based Antifreeze concentrates on ethylene glycol or Propylene glycol or mixtures of alkylene glycols or of Glycerin with ethylene glycol or propylene glycol, each at least 95% by weight of ethylene glycol and / or propylene glycol and / or Contain glycerin.
  • the antifreeze concentrates according to the invention can be used as further conventional aids in usual small amounts Defoamers (usually in amounts of 0.003 to 0.008% by weight) as well as for reasons of hygiene and safety in the event of a Ingestion contains bitter substances (e.g. denatonium benzoate).
  • Defoamers usually in amounts of 0.003 to 0.008% by weight
  • bitter substances e.g. denatonium benzoate
  • the present invention also relates to ready-to-use aqueous coolant compositions with a low freezing point, especially for the cooler protection of internal combustion engines in the automotive sector, which water and 10 to 90 wt .-%, in particular 20 to 60% by weight of the antifreeze concentrates according to the invention include.
  • a commercially available antifreeze concentrate was used for the experiments based on ethylene glycol with a mixture of Adipic acid, sebacic acid and tolutriazole as inhibitor components used.
  • Tables 2 and 3 show the good results of a formulation according to the invention with 50 ppm CI Reactive Violet 5 in the glassware corrosion test in accordance with ASTM D 1384-97 and in the heat transfer corrosion test in accordance with ASTM D 4340. The tests were also able to show that the The dye in the formulation was stable even at high temperatures and no discoloration of the coolant was observed. Hot plate test dye CI no. CAS-No.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)
  • Medicinal Preparation (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP02740549A 2001-05-10 2002-05-02 Gefrierschutzmittelkonzentrate enthaltend den farbstoff c.i. reactive violet 5 Expired - Lifetime EP1390438B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10122769A DE10122769A1 (de) 2001-05-10 2001-05-10 Gefrierschutzmittelkonzentrate enthaltend den Farbstoff C.I. Reactive Violet 5
DE10122769 2001-05-10
PCT/EP2002/004784 WO2002090462A1 (de) 2001-05-10 2002-05-02 Gefrierschutzmittelkonzentrate enthaltend den farbstoff c.i. reactive violet 5

Publications (2)

Publication Number Publication Date
EP1390438A1 EP1390438A1 (de) 2004-02-25
EP1390438B1 true EP1390438B1 (de) 2004-11-24

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EP02740549A Expired - Lifetime EP1390438B1 (de) 2001-05-10 2002-05-02 Gefrierschutzmittelkonzentrate enthaltend den farbstoff c.i. reactive violet 5

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US (1) US6818147B2 (cs)
EP (1) EP1390438B1 (cs)
JP (1) JP2004530017A (cs)
KR (1) KR20040002940A (cs)
CN (1) CN1219845C (cs)
AR (1) AR033472A1 (cs)
AT (1) ATE283328T1 (cs)
BR (1) BR0209293B1 (cs)
CA (1) CA2445792C (cs)
CZ (1) CZ299952B6 (cs)
DE (2) DE10122769A1 (cs)
ES (1) ES2233830T3 (cs)
HU (1) HU229647B1 (cs)
MX (1) MXPA03009001A (cs)
NO (1) NO333717B1 (cs)
PL (1) PL200841B1 (cs)
PT (1) PT1390438E (cs)
SK (1) SK286675B6 (cs)
WO (1) WO2002090462A1 (cs)
ZA (1) ZA200309538B (cs)

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CA2546332A1 (en) * 2003-11-13 2005-05-26 Vladisav Milovanovic The nontoxic watery solution against freezing and corrosion and the regenerator for the utilized antifreeze
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RU2007112833A (ru) 2004-09-08 2008-10-20 Хонейвелл Интернэшнл Инк. (Us) Ионообменные смолы, способ их получения, устройства и агрегаты теплопередачи, содержащие их
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CN101899287B (zh) * 2010-07-16 2015-08-26 中国石油化工股份有限公司 太阳能集热管导热液
DE102012022246B4 (de) * 2012-11-14 2014-07-10 Sew-Eurodrive Gmbh & Co Kg Vorrichtung, aufweisend ein Gehäuseteil und ein weiteres Teil
JP6391598B2 (ja) * 2013-02-13 2018-09-19 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 防食性を有する凍結防止濃縮物およびそれから製造される水性冷却剤組成物
US9540558B2 (en) 2013-06-12 2017-01-10 Ashland Licensing And Intellectual Property, Llc Extended operation engine coolant composition
JP6339442B2 (ja) * 2014-08-01 2018-06-06 シーシーアイ株式会社 着色冷却液組成物
CN104250545B (zh) * 2014-10-16 2017-06-06 诺泰生物科技(合肥)有限公司 一种甘油基防冻液
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KR20040002940A (ko) 2004-01-07
ZA200309538B (en) 2005-02-23
WO2002090462A1 (de) 2002-11-14
ATE283328T1 (de) 2004-12-15
DE10122769A1 (de) 2002-11-14
MXPA03009001A (es) 2004-02-12
NO333717B1 (no) 2013-09-02
CA2445792C (en) 2010-04-27
CN1507486A (zh) 2004-06-23
HUP0400093A2 (hu) 2004-04-28
SK13702003A3 (sk) 2004-04-06
JP2004530017A (ja) 2004-09-30
BR0209293B1 (pt) 2012-06-26
CZ20032949A3 (cs) 2004-02-18
PL366454A1 (en) 2005-02-07
BR0209293A (pt) 2004-07-13
CN1219845C (zh) 2005-09-21
HUP0400093A3 (en) 2012-05-29
DE50201627D1 (de) 2004-12-30
NO20034959D0 (no) 2003-11-07
NO20034959L (no) 2003-11-07
AR033472A1 (es) 2003-12-17
SK286675B6 (sk) 2009-03-05
CZ299952B6 (cs) 2009-01-07
US20040119044A1 (en) 2004-06-24
PL200841B1 (pl) 2009-02-27
CA2445792A1 (en) 2002-11-14
US6818147B2 (en) 2004-11-16
PT1390438E (pt) 2005-04-29
ES2233830T3 (es) 2005-06-16
HU229647B1 (en) 2014-03-28
EP1390438A1 (de) 2004-02-25

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